CN101664685A - Low-platinum high active core-shell structure catalyst and preparation method thereof - Google Patents
Low-platinum high active core-shell structure catalyst and preparation method thereof Download PDFInfo
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- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 12
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- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000428 dust Substances 0.000 claims description 8
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- 229910052718 tin Inorganic materials 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
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- 239000004280 Sodium formate Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 7
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 7
- 235000019254 sodium formate Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
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- 235000019256 formaldehyde Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 3
- 239000000446 fuel Substances 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
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- 229910021393 carbon nanotube Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 241000370738 Chlorion Species 0.000 description 5
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- 241000894007 species Species 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides a high active core-shell structure catalyst used for low temperature fuel cell. The preparation method comprises the following steps: adopting carbon powder or carbon nanotubesas carrier, coating single-layer or two-layer platinum which is reduced by reductant, on the metal-based core to form a core-shell structure and loading the structure on carbon powder or carbon nanotubes carrier. The catalyst has low platinum loading and high catalytic activity so that platinum loading is low, the activity of the catalyst is high; the contradiction between the cost and performanceof catalyst is effectively solved, and the high active core-shell structure catalyst plays an extremely important role in solving the current problems of the fuel cell.
Description
Technical field
The invention belongs to the chemical energy source technical field, relate to a kind of catalyst that is used for fuel cell, relate in particular to a kind of low-platinum high active core-shell structure catalyst that is used for low-temperature fuel cell and preparation method thereof.
Background technology
The environmental problem that causes along with fossil fuel such as energy problem and coal combustion severe day by day more and more obtains the great attention of countries in the world government and scientific circles about the research and development of hydrogen energy source and fuel cell.Fuel cell technology has the energy conversion efficiency height, significant advantage such as ambient influnence little (zero-emission or low emission), fuel source be rich and varied is considered to a kind of most possible extensive novel energy technology that substitutes the existing energy with it, is to solve future source of energy problem and because one of important technical of the burning serious problem of environmental pollution that fossil energy caused.Wherein low-temperature fuel cell owing to its have the specific energy height, pollution-free, advantage such as cold-starting is subjected to paying close attention to widely fast.Low-temperature fuel cell comprises Proton Exchange Membrane Fuel Cells, direct fuel liquid battery etc.Although fuel cell has development potentiality very much theoretically, and obtained bigger progress aspect research, its commercialization still is faced with lot of challenges.The present employed catalyst of low-temperature fuel cell is mostly based on noble metal platinum, and the price of platinum is very expensive owing to the restriction that is subjected to resource, makes the catalyst cost occupy very big proportion in the fuel cell totle drilling cost.How on the basis that does not reduce catalyst catalytic performance, reducing the carrying capacity of platinum and then reducing the catalyst price becomes a challenging problem.The low-platinum catalyst of development of new has crucial meaning for solving the present problem that exists of fuel cell.Find a kind of more better than pure platinum, the catalytic activity catalyst becomes a focus in the current fuel cell studies efficiently.
Summary of the invention
The purpose of this invention is to provide a kind of low-platinum high active core-shell structure catalyst that is used for low-temperature fuel cell and preparation method thereof.
The preparation method of low-platinum high active core-shell structure catalyst of the present invention comprises following two steps:
(1) with zinc, the chloride of one or both metals or nitrate are dissolved in the ethylene glycol in iron, palladium, tin, cobalt, nickel, the copper, add the natrium citricum of 2～2.5 times of the amounts of total metal ion species, ultrasonic it are dissolved fully; Regulate pH to 8～12 with the KOH/ ethylene glycol solution of mass concentration 5%, add the sodium formate of 1～5 times of the amount of total metal ion species, add the carbon dust or the CNT of 4～8 times of the theoretical total metal qualities in reduction back again, stir ultrasonic being uniformly dispersed down; Reacted 4～10 hours down in 140～200 ℃, wash with water, drying obtains the catalyst precursor.
When the chloride of selecting two kinds of metals for use or nitrate, the two is dissolved in the ethylene glycol with 1: 0.3～1: 3 mass ratio.
(2) the 20mg/ml chloroplatinic acid is dissolved in the ethylene glycol, regulates pH to 8～12 with the KOH/ ethylene glycol solution of mass concentration 4～5%; The reducing agent that adds 1～10 times of chloroplatinic acid amount of substance, ultrasonic dispersion adds the catalyst precursor of aforementioned preparation again, under agitation in 60～150 ℃ of following reduction reactions 2～6 hours; Cooling was left standstill 1～4 hour; Suction filtration, washing, drying obtains the catalyst of low-platinum high active core-shell structure.
Described reducing agent is ethylene glycol, sodium borohydride, formic acid, formaldehyde or ascorbic acid; The addition of described catalyst precursor is 5～50 times of the theoretical platinum quality in reduction back.
The low-platinum high active core-shell structure catalyst of the present invention's preparation, be that platinum simple substance after the reduction covers the surface of metallic zinc, iron, palladium, tin, cobalt, nickel, copper or its bimetallic alloy, formation is shell with platinum, be the nucleocapsid structure of kernel with metallic zinc, iron, palladium, tin, cobalt, nickel, copper or its bimetallic alloy, and be carried on jointly on carbon dust or the CNT.The quality of platinum is 1～15% of a catalyst total amount, and the quality of core-shell structure metall is 10～60% of a catalyst gross mass.
When described kernel was bimetallic alloy, the mass ratio of two kinds of metals was 5: 1～1: 5.
Be example with the PdFe@Pt/C catalyst below, the structure and the performance of the low-platinum high active core-shell structure catalyst of the present invention's preparation is described.
Among Fig. 1, (B) be PdFe@Pt/C TEM figure, (A) PdFe/C catalyst TEM figure.As can be seen from Figure 1, catalyst is comparatively even in the carbon dust surface distributed.We add up its particle size, find that PdFe/C catalyst (A) and PdFe@Pt/C catalyst particle size size are approximately respectively about 4.8nm and 5.3nm, therefore, the particle diameter that carries the catalyst behind the platinum has the phenomenon of apparent in view increase, illustrate that the platinum after the reduction has deposited to the surface of the kernel of Pd-Fe formation.
Fig. 2 is the XRD figure of PdFe@Pt/C catalyst.And with the Pt/C commercial catalysts, Pd/C, the XRD figure of PdFe/C catalyst compares.The PdFe@Pt/C catalyst is the same with other catalyst does not as can be seen from Figure 2 have other diffraction maximum to occur, and shows that the PdFe@Pt/C catalyst also is a phase structure.Wide diffraction maximum shows that alloy catalyst has smaller particle size and good dispersiveness among the figure.At 40 °, 46.7 °, 70 ° of (111) of representing the catalyst of face-centred cubic structure respectively, (200) and (220) crystal face.Its (111) crystal face is carried out integration, according to Scherrer formula: B
2 θ=0.94 λ/rcos θ calculates the particle size of the active component that can get them: the Pt/C commercial catalysts is 3.1nm, Pd/C is 6nm, PdFe/C is 4.8nm, active component is a composite construction in the PdFe@Pt/C catalyst, use the Jade software analysis, about 1～2 atomic layer of shell, overall diameter is about 5.2nm, and this is almost consistent with the result that TEM obtains.
Fig. 3 is that Pt/C commercial catalysts and PdFe@Pt/C catalyst are at the saturated 0.5M H of oxygen
2SO
4Solution neutral line scanning curve, sweep speed: 5mV/s; Rotating speed: 1600rpm.As a comparison, with the synthetic Pd/C of similar approach, the linear scan of PdFe/C catalyst is the result also list in wherein.As can be seen from Figure 3, the PdFe@Pt/C catalyst is compared with other several catalyst, has best hydrogen reduction electro catalytic activity, current density at dynamics Controlling district per unit mass platinum obviously increases, compare hydrogen reduction half current potential of Pd@Pt/C catalyst about 20mV that shuffled with commercial Pt/C.And the ORR diffusion current density of PdFe@Pt/C catalyst enlarges markedly, and illustrates that it has better hydrogen reduction catalytic activity than commercial Pt/C catalyst.
Fig. 4 is commercial catalysts Pt/C and the mass activity electric current comparison diagram of PdFe@Pt/C catalyst when 0.4V and 0.5V (with respect to the Ag/AgCl electrode, the roughly operating potential of fuel cell).Can see that by Fig. 4 PdFe@Pt/C catalyst unit platinum mass activity electric current is 126mAmg when 0.4V and 0.5V
Pt -1With 125mA mg
Pt -1, approximately be 4 times of commercial Pt/C catalyst and 5 times (commercial Pt/C catalyst unit platinum mass activity electric current 30mA mg only arranged
Pt -1With 22.5mA mg
Pt -1).This shows that the PdFe@Pt/C catalyst of the present invention's preparation makes the utilization rate of platinum obtain effective lifting.
Have very high catalytic activity equally through a large amount of catalyst that experiment showed, other nucleocapsid structures that the present invention prepares, fully can be as the electrode catalyst of fuel cell.
The present invention compared with prior art has the following advantages:
1, the present invention is with zinc, iron, palladium, tin, cobalt, nickel, copper simple substance or its pairing gold are kernel, simple substance platinum behind the reducing agent is covered core surface by the mode that deposits, and be carried on carbon dust or the CNT, formation is shell with platinum, with metallic zinc, iron, palladium, tin, cobalt, nickel, copper or its bimetallic alloy are the nucleocapsid structure of kernel, under low platinum carrying capacity, obtain high catalytic activity catalyst, the low carrying capacity of platinum and the high activity of catalyst have been realized, effectively solved the cost of platinum based catalyst and the contradiction between the performance, had crucial meaning for solving the present problem that exists of fuel cell.
2, Preparation of catalysts technology of the present invention is simple, with short production cycle, and easy control of reaction conditions is suitable for industrialization promotion production.
Description of drawings
Fig. 1 is the TEM figure of PdFe/C catalyst (A) and PdFe@Pt/C catalyst (B)
Fig. 2 is the Pt/C commercial catalysts, Pd/C, the XRD figure of PdFe/C and PdFe@Pt/C catalyst.
Fig. 3 is the Pt/C commercial catalysts, Pd/C, and PdFe/C and PdFe@Pt/C catalyst are at the saturated 0.5M H of oxygen
2SO
4Solution neutral line scanning curve, sweep speed: 5mV/s; Rotating speed: 1600rpm.
Fig. 4 is commercial catalysts Pt/C and the mass activity map of current of PdFe@Pt/C catalyst when 0.4V and 0.5V.
The specific embodiment
Embodiment 1:Pd@Pt/C Preparation of catalysts
Palladium bichloride 42.9mg is joined in the 50ml round-bottomed flask, add 25ml ethylene glycol, add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully.Add the 193.8mg natrium citricum, be stirred to dissolving fully after, be 9 with the pH value of 5%KOH/EG solution regulator solution; Add sodium formate 102.8mg, carbon dust 100mg stirred ultrasonic 0.5 hour 0.5 hour; Gained liquid was transferred in the autoclave, places baking oven, in 160 ℃ of reactions 8 hours; The gains suction filtration detects less than till the chlorion to solution with three water washings, and 70 ℃ of vacuum drying obtain catalyst precarsor to weight.
Take by weighing chloroplatinic acid 17.0mg, add round-bottomed flask, and add 20ml ethylene glycol (ethylene glycol is solvent, also is reducing agent simultaneously), with pH value=9 of 5%KOH/EG solution regulator solution; The catalyst precarsor 50mg that adds aforementioned preparation under agitation reacted 6 hours in 60 ℃, and cooling is left standstill more than the 4h.With three heavy water cyclic washings, drying obtains the Pd@Pt/C catalyst behind the suction filtration.
After measured, in the Pd@Pt/C catalyst, Pt accounts for 5% of catalyst gross mass; Pd accounts for 20% of catalyst gross mass.The particle size 4.4nm of active component compares with commercial Pt/C, hydrogen reduction half current potential of Pd@Pt/C catalyst about 8mV that shuffled.
Embodiment 2:PdFe@Pt/C Preparation of catalysts
Palladium bichloride 19.2mg and iron chloride 106.0mg are joined in the 50ml round-bottomed flask of 25ml ethylene glycol, and magneton stirs, and ultrasonicly makes its all dissolving fully more than 0.5 hour; Add the 294.3mg natrium citricum, be stirred to dissolving fully.With the PH=10 of 5%KOH/EG solution regulator solution, add sodium formate 156.2mg, CNT 100mg stirred ultrasonic 0.5 hour 0.5 hour.
Above-mentioned solution is transferred in the autoclave, placed baking oven, reacted 8 hours down in 160 ℃.The gains suction filtration detects less than till the chlorion to solution with three water washings, to weight, gets catalyst precarsor in 70 degree vacuum drying.
Take by weighing the 9.4mg chloroplatinic acid, add round-bottomed flask, and add 20ml ethylene glycol, the pH value of 5%KOH/EG solution regulator solution is an alkalescence 9, adds the formic acid of 1ml, adds the catalyst precarsor 50mg of above-mentioned preparation, under agitation reacted 4 hours in 60 ℃, cooling is left standstill more than the 4h.With three heavy water cyclic washings, drying gets the PdFe@Pt/C catalyst behind the suction filtration.
After measured, in the PdFe@Pt/C catalyst, Pt accounts for 4.4% of catalyst gross mass; Pd accounts for 12% of catalyst gross mass, and Fe accounts for 11% of catalyst gross mass.The particle size 4.6nm of active component compares with commercial Pt/C, hydrogen reduction half current potential of Pd@Pt/C catalyst about 17mV that shuffled.
Embodiment 3:PdCo@Pt/C Preparation of catalysts
Palladium bichloride 36.3mg and cobalt chloride 32.3mg are joined in the 50ml round-bottomed flask, add 25ml ethylene glycol again, magneton stirs, and ultrasonicly makes its all dissolving fully more than 0.5 hour; Add the 232.0mg natrium citricum, be stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is 9, adds sodium formate 123.12mg, adds carbon dust 100mg, stirs ultrasonic 0.5 hour 0.5 hour; Solution is transferred in the autoclave, places baking oven, reacts 8 hours down in 160 ℃.The gains suction filtration detects less than till the chlorion to solution with three water washings, to weight, gets catalyst precarsor in 70 degree vacuum drying.
Take by weighing the 8.9mg chloroplatinic acid, add round-bottomed flask, and add 20ml ethylene glycol, pH value with 5%KOH/EG solution regulator solution is an alkalescence 10, adds the formaldehyde of 1ml, adds the catalyst precarsor 50mg of above-mentioned preparation, under agitation reacted 2 hours in 80 ℃, cooling is left standstill more than the 4h.With three heavy water cyclic washings, drying gets the PdCo@Pt/C catalyst behind the suction filtration.
After measured, in the PdCo@Pt/C catalyst, Pt accounts for 3.6% of catalyst gross mass; Pd accounts for 12% of catalyst gross mass, and Co accounts for 14% of catalyst gross mass.The particle size 4.7nm of active component compares with commercial Pt/C, hydrogen reduction half current potential of Pd@Pt/C catalyst about 11mV that shuffled.
Embodiment 4:PdCu@Pt/C Preparation of catalysts
Palladium bichloride 36.1mg and copper chloride 34.7mg are joined in the 50ml round-bottomed flask, add 25ml ethylene glycol again, magneton stirs, and ultrasonicly makes its all dissolving fully more than 0.5 hour; Add the 239.4mg natrium citricum, be stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is 9, adds sodium formate 126.8mg, adds CNT 100mg, stirs ultrasonic 0.5 hour 0.5 hour.
Above-mentioned solution is transferred in the autoclave, placed baking oven, reacted 8 hours down in 160 ℃.The gains suction filtration detects less than till the chlorion to solution with three water washings, to weight, gets catalyst precarsor in 70 degree vacuum drying.
Taking by weighing the 8.2mg chloroplatinic acid, add round-bottomed flask, and add 20ml ethylene glycol, is 9 with the pH value of 5%KOH/EG solution regulator solution; Add the 40mg ascorbic acid, add the catalyst precarsor 50mg of above-mentioned preparation, under agitation reacted 2 hours in 80 ℃, cooling is left standstill more than the 4h; With three heavy water cyclic washings, drying gets the PdCu@Pt/C catalyst behind the suction filtration.
After measured, in the PdCu@Pt/C catalyst, Pt accounts for 4.5% of catalyst gross mass; Pd accounts for 15% of catalyst gross mass, and Cu accounts for 11% of catalyst gross mass.The particle size 5.2nm of active component compares with commercial Pt/C, hydrogen reduction half current potential of Pd@Pt/C catalyst about 16mV that shuffled.
Embodiment 5:PdNi@Pt/C Preparation of catalysts
Palladium bichloride 36.6mg and cobalt chloride 45.9mg are joined in the 50ml round-bottomed flask, add 25ml ethylene glycol again, magneton stirs, and ultrasonicly makes its all dissolving fully more than 0.5 hour, adds the 243..1mg natrium citricum, is stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is 10, adds sodium formate 129.0mg, adds CNT 100mg, stirs ultrasonic 0.5 hour 0.5 hour.Above-mentioned solution is transferred in the autoclave, placed baking oven, reacted 8 hours down in 160 ℃.The gains suction filtration detects less than till the chlorion to solution with three water washings, to weight, gets catalyst precarsor in 70 degree vacuum drying.
Taking by weighing the 8.6mg chloroplatinic acid, add round-bottomed flask, and add 20ml ethylene glycol, is 10 with the pH value of 5%KOH/EG solution regulator solution; Add sodium borohydride 40mg, ultrasonic dispersion.The catalyst precarsor 50mg that adds above-mentioned preparation more under agitation reacted 2 hours in 80 ℃, and cooling is left standstill more than the 4h.With three heavy water cyclic washings, drying gets the PdNi@Pt/C catalyst behind the suction filtration.
After measured, in the PdNi@Pt/C catalyst, Pt accounts for 4.4% of catalyst gross mass; Pd accounts for 15% of catalyst gross mass, and Ni accounts for 12% of catalyst gross mass.The particle size 4.8nm of active component compares with commercial Pt/C, hydrogen reduction half current potential of Pd@Pt/C catalyst about 12mV that shuffled.
Claims (6)
1, a kind of preparation method of low-platinum high active core-shell structure catalyst comprises following two steps:
(1) with zinc, the chloride of one or both metals or nitrate are dissolved in the ethylene glycol in iron, palladium, tin, cobalt, nickel, the copper, add the natrium citricum of 2～2.5 times of the amounts of total metal ion species, ultrasonic it are dissolved fully; Regulate pH to 8～12 with the KOH/ ethylene glycol solution of mass concentration 5%, add the sodium formate of 1～5 times of the amount of total metal ion species again, add the carbon dust or the CNT of 4～8 times of the theoretical total metal qualities in reduction back again, stir ultrasonic being uniformly dispersed in back; Reacted 4～10 hours down in 140～200 ℃, wash with water, drying obtains the catalyst precursor;
(2) chloroplatinic acid with 20mg/ml is dissolved in the ethylene glycol, regulates pH to 8～12 with the KOH/ ethylene glycol solution of mass concentration 4～5%; The reducing agent that adds 1～10 times of chloroplatinic acid amount of substance ultrasonicly disperses it, adds the catalyst precursor of aforementioned preparation again, under agitation in 60～150 ℃ of following reduction reactions 2～6 hours; Cooling was left standstill 1～4 hour; Suction filtration, washing, drying obtains the catalyst of low-platinum high active core-shell structure; The addition of described catalyst precursor is 5～50 times of the theoretical platinum quality in reduction back.
2, the preparation method of low-platinum high active core-shell structure catalyst according to claim 1, it is characterized in that: the chloride of described two kinds of metals or nitrate are dissolved in the ethylene glycol with 1: 0.3～1: 3 amount ratio.
3, the preparation method of low-platinum high active core-shell structure catalyst according to claim 1, it is characterized in that: described reducing agent is ethylene glycol, sodium borohydride, formic acid, formaldehyde or ascorbic acid.
4, the low-platinum high active core-shell structure catalyst of method preparation according to claim 1, it is characterized in that: the platinum after the reduction covers the surface of metallic zinc, iron, palladium, tin, cobalt, nickel, copper or its bimetallic alloy, formation is shell with platinum, be the nucleocapsid structure of kernel with metallic zinc, iron, palladium, tin, cobalt, nickel, copper or its bimetallic alloy, and be carried on jointly on carbon dust or the CNT.
5, as the low-platinum high active core-shell structure catalyst of method preparation as described in the claim 4, it is characterized in that: the quality of described platinum is 1～15% of a catalyst total amount, and the quality of core-shell structure metall is 10～60% of a catalyst gross mass.
6, as the low-platinum high active core-shell structure catalyst of method preparation as described in the claim 3, it is characterized in that: when described kernel was bimetallic alloy, the mass ratio of two kinds of metals was 5: 1～1: 5.
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